CN102725353B - Thermoplastic elastomer composition and manufacturing method therefor - Google Patents
Thermoplastic elastomer composition and manufacturing method therefor Download PDFInfo
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- CN102725353B CN102725353B CN201180007088.4A CN201180007088A CN102725353B CN 102725353 B CN102725353 B CN 102725353B CN 201180007088 A CN201180007088 A CN 201180007088A CN 102725353 B CN102725353 B CN 102725353B
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- thermoplastic elastomer
- polyamide resin
- composition
- halogenation
- nylon
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- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 229920001971 elastomer Polymers 0.000 claims abstract description 68
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 67
- 239000005060 rubber Substances 0.000 claims abstract description 65
- 229920001577 copolymer Polymers 0.000 claims abstract description 55
- 239000004593 Epoxy Substances 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 238000002844 melting Methods 0.000 claims abstract description 24
- 230000008018 melting Effects 0.000 claims abstract description 24
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 230000026030 halogenation Effects 0.000 claims description 44
- 238000005658 halogenation reaction Methods 0.000 claims description 44
- 238000002156 mixing Methods 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 238000004132 cross linking Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 229920000577 Nylon 6/66 Polymers 0.000 claims description 6
- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 claims description 6
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 4
- 229920000299 Nylon 12 Polymers 0.000 claims description 4
- 230000031709 bromination Effects 0.000 claims description 4
- 238000005893 bromination reaction Methods 0.000 claims description 4
- 229920002292 Nylon 6 Polymers 0.000 claims description 3
- 229920000571 Nylon 11 Polymers 0.000 claims description 2
- 229920003189 Nylon 4,6 Polymers 0.000 claims description 2
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 2
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 2
- 229920003233 aromatic nylon Polymers 0.000 claims description 2
- YWJUZWOHLHBWQY-UHFFFAOYSA-N decanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCC(O)=O YWJUZWOHLHBWQY-UHFFFAOYSA-N 0.000 claims description 2
- ZMUCVNSKULGPQG-UHFFFAOYSA-N dodecanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCCCC(O)=O ZMUCVNSKULGPQG-UHFFFAOYSA-N 0.000 claims description 2
- 238000004898 kneading Methods 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 8
- -1 Zinic stearas Chemical compound 0.000 description 7
- 235000021355 Stearic acid Nutrition 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000008117 stearic acid Substances 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 150000003440 styrenes Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000000873 masking effect Effects 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- VXPSQDAMFATNNG-UHFFFAOYSA-N 3-[2-(2,5-dioxopyrrol-3-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C(=CC=CC=2)C=2C(NC(=O)C=2)=O)=C1 VXPSQDAMFATNNG-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- NOAHDRRLJOCQGN-UHFFFAOYSA-N C(C1CO1)OCC(=S)OCCO Chemical compound C(C1CO1)OCC(=S)OCCO NOAHDRRLJOCQGN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241000863032 Trieres Species 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- 238000012001 immunoprecipitation mass spectrometry Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- KHMYONNPZWOTKW-UHFFFAOYSA-N pent-1-enylbenzene Chemical compound CCCC=CC1=CC=CC=C1 KHMYONNPZWOTKW-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0008—Compositions of the inner liner
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2415/00—Characterised by the use of rubber derivatives
- C08J2415/02—Rubber derivatives containing halogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T152/00—Resilient tires and wheels
- Y10T152/10—Tires, resilient
- Y10T152/10495—Pneumatic tire or inner tube
Landscapes
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
- Epoxy Resins (AREA)
Abstract
Disclosed is a thermoplastic elastomer composition that has a continuous phase and a dispersed phase, with the continuous phase containing an epoxy-modified polyamide resin (A) and the dispersed phase containing a halogenated isoolefin-para-alkylstyrene copolymer rubber (B). Said thermoplastic elastomer composition is characterized by being obtained by melt-kneading the following at a temperature greater than or equal to the melting point of a polyamide resin (C): a halogenated isoolefin-para-alkylstyrene copolymer rubber (B); the aforementioned polyamide resin (C); and at least 0.05 mass parts and less than 3 mass parts, per 100 mass parts of the polyamide resin (C), of a polyfunctional epoxy compound (D), each molecule of which has at least two epoxy groups. The thermoplastic elastomer composition is further characterized in that the epoxy-modified polyamide resin (A) is generated by a reaction between the polyamide resin (C) and the polyfunctional epoxy compound (D) during the aforementioned melt-kneading.
Description
Technical field
The present invention relates to composition for thermoplastic elastomer, in more detail, relate to the pneumatic tyre that the composition for thermoplastic elastomer of tired old weather resistance and excellent in workability and its manufacture method and air retaining wall are used this composition for thermoplastic elastomer.
Background technology
Specific rubber elastomer composition is dispersed in composition for thermoplastic elastomer in specific thermoplastic resin external phase, resistance to ventilation property and flexibility balance excellence known (Japanese kokai publication hei 8-259741 communique) as discontinuous phase.In addition, by making the melt viscosity (η of the thermoplastic resin composition in composition for thermoplastic elastomer
m) and the melt viscosity (η of rubber elastomer composition
d) and poor (the Δ SP) of the solubility parameters of rubber elastomer composition and thermoplastic resin composition meet specific relational expression and realize high-elastic gonosome component ratio, obtain being thus more rich in flexibility, the composition for thermoplastic elastomer of resistance to gas-premeable excellence, and the pneumatic tyre of using it for permeation-proof gas-bearing formation also known (Japanese kokai publication hei 10-25375 communique).And then, by using thermoplastic resin as external phase, using and have the barrier resins composition with the phase structure of disperseing with flats in the thermoplastic elastomer of rubber combination as disperse phase, thereby the resistance to ventilation property obtaining improves and has flexibility, oil-proofness, winter hardiness and a stable on heating composition for thermoplastic elastomer also known (Japanese kokai publication hei 10-114840 communique).And then, by stratiform Modification of Clay Minerals polyamide resin in disperseed dynamic crosslinking halogenation isomeric olefine-to the composition for thermoplastic elastomer of alkylstyrene copolymers also known (TOHKEMY 2000-160024 communique).
Summary of the invention
The problem that invention will solve
Dynamic crosslinking composition for thermoplastic elastomer for polyamide resin and halogenation isomeric olefine-for alkylstyrene copolymers rubber, known, halogenation isomeric olefine-disperse volumetric ratio more tiny, that fill with respect to polyamide resin in addition higher to alkylstyrene copolymers rubber in polyamide resin, just can obtain the dynamic crosslinking composition for thermoplastic elastomer that tired old weather resistance (resistance to fatigue) is higher.But due to halogenation isomeric olefine-alkylstyrene copolymers rubber is reacted with polyamide resin, so halogenation isomeric olefine-disperse more tiny to alkylstyrene copolymers rubber, the volumetric ratio of filling with respect to polyamide resin is in addition higher, the halogenation isomeric olefine contacting with polyamide resin-just larger to the total area at the interface of alkylstyrene copolymers rubber particles, accompany therewith, unit volume and halogenation isomeric olefine polyamide resin molecular reaction-alkylstyrene copolymers rubber molecule quantity is increased, result, the mobility of melting mixing thing reduces, there is processibility (mixing property, thermostability, masking etc.) problem significantly reducing.
The means of dealing with problems
The inventor is studied repeatedly in order to solve above-mentioned problem, found that, by when polyamide resin and halogenation isomeric olefine-to alkylstyrene copolymers rubber melting mixing, by the multi-functional epoxy compound who makes polyamide resin and every 1 molecule there are 2 above epoxy group(ing), react, become epoxide-modifying polyamide resin, can obtain the composition for thermoplastic elastomer that tired old excellent in te pins of durability and processibility (mixing property, thermostability, masking etc.) are excellent, thereby complete the present invention.
The invention provides a kind of composition for thermoplastic elastomer, it has external phase and disperse phase, external phase contains (A) epoxide-modifying polyamide resin, disperse phase contains (B) halogenation isomeric olefine-to alkylstyrene copolymers rubber, this composition for thermoplastic elastomer is characterised in that, is by inciting somebody to action
(B) halogenation isomeric olefine-to alkylstyrene copolymers rubber,
(C) polyamide resin and
(D) with respect to 100 mass parts polyamide resins (C) be 0.05 mass parts above and be less than 3 mass parts, every 1 molecule has the multi-functional epoxy compounds of 2 above epoxy group(ing)
Melting mixing at temperature more than the fusing point of polyamide resin (C), thereby obtain,
Epoxide-modifying polyamide resin (A) is by the reaction between polyamide resin (C) and multi-functional epoxy compound (D), to generate in described melting mixing.
The present invention also provides a kind of manufacture method of composition for thermoplastic elastomer, described composition for thermoplastic elastomer has external phase and disperse phase, external phase contains (A) epoxide-modifying polyamide resin, disperse phase contains (B) halogenation isomeric olefine-to alkylstyrene copolymers rubber, described manufacture method is characterised in that, comprises following operation: will
(B) halogenation isomeric olefine-to alkylstyrene copolymers rubber,
(C) polyamide resin and
(D) with respect to 100 mass parts polyamide resins (C) be 0.05 mass parts above and be less than 3 mass parts, every 1 molecule has the multi-functional epoxy compounds of 2 above epoxy group(ing)
Melting mixing at temperature more than the fusing point of polyamide resin (C).
Invention effect
The present invention by making polyamide resin react with the multi-functional epoxy compound that every 1 molecule has more than 2 epoxy group(ing) when polyamide resin and halogenation isomeric olefine-to alkylstyrene copolymers rubber melting mixing, become epoxide-modifying polyamide resin, the composition for thermoplastic elastomer of tired old weather resistance and excellent in workability can be provided.In addition, composition for thermoplastic elastomer of the present invention, as mentioned above, not only tired old weather resistance and excellent in workability, and there is the excellent barrier properties for gases from polyamide resin.
Embodiment
In composition for thermoplastic elastomer of the present invention, epoxide-modifying polyamide resin (A) forms external phase, halogenation isomeric olefine-alkylstyrene copolymers rubber (B) is formed to disperse phase., halogenation isomeric olefine-alkylstyrene copolymers rubber (B) the is form of discontinuous dispersion in the external phase that contains epoxide-modifying polyamide resin (A).
The epoxide-modifying polyamide resin (A) that forms external phase in composition for thermoplastic elastomer of the present invention is by by polyamide resin (C), halogenation isomeric olefine-to alkylstyrene copolymers rubber (B), with with respect to polyamide resin (C) 100 mass parts, be 0.05 mass parts every 1 molecule above and that be less than 3 mass parts there are 2 above epoxy group(ing) the temperature of multi-functional epoxy compound (D) more than the fusing point of polyamide resin (C) under when melting mixing, between polyamide resin (C) and multi-functional epoxy compound (D), react and generate.
As the example of polyamide resin (C), can list nylon-type, such as nylon 11, nylon 12, nylon 6, nylon 66, nylon 6/66, nylon 6/12, nylon 6/10, nylon 4/6, nylon 6/66/12, aromatic nylon etc.Polyamide resin (C), both can be in these polyamide resins a kind forms, also can consist of two or more.As polyamide resin (C), from the viewpoint of having tired old weather resistance and barrier properties for gases concurrently, preferred nylon 6, nylon 6/66.
The halogenation isomeric olefine using in the present invention-to alkylstyrene copolymers rubber (B), can be by for example making isomeric olefine and the multipolymer halogenation of ring-alkylated styrenes being manufactured.Isomeric olefine and the ratio of mixture of ring-alkylated styrenes, the polymerization degree, molecular-weight average, polymeric species (segmented copolymer, random copolymers etc.), viscosity, halogen atom etc. are not particularly limited, those skilled in the art can select according to desired physical property of composition for thermoplastic elastomer etc.Example as forming halogenation isomeric olefine-to the isomeric olefine of alkylstyrene copolymers rubber (B), can list, iso-butylene, isopentene, dissident's alkene etc., and as isomeric olefine, preferred iso-butylene.As the example to ring-alkylated styrenes that forms halogenation isomeric olefine-to alkylstyrene copolymers rubber (B), can list p-methylstyrene, to ethyl styrene, to propylstyrene, to butylstyrene etc., as to the preferred p-methylstyrene of ring-alkylated styrenes.Halogen as forming halogenation isomeric olefine-to alkylstyrene copolymers rubber (B), can list fluorine, chlorine, bromine, iodine, as the preferred bromine of halogen.Halogenation isomeric olefine-be bromination polyisobutene-p-methylstyrene copolymer rubber to alkylstyrene copolymers rubber particularly preferably.Bromination iso-butylene-p-methylstyrene copolymer rubber can obtain with the trade(brand)name of Exxpro (registered trademark) from エ Network ソ Application モ mono-ビル ケミカル company (ExxonMobil Chemical Company).
Halogenation isomeric olefine-to alkylstyrene copolymers rubber (B) preferably dynamic crosslinking.By dynamic crosslinking, can make the external phase of composition for thermoplastic elastomer and disperse phase fix.Dynamic crosslinking can by by polyamide resin (C), halogenation isomeric olefine-to alkylstyrene copolymers rubber (B) and with respect to polyamide resin (C) 100 mass parts be 0.05 mass parts every 1 molecule above and that be less than 3 mass parts there are 2 above epoxy group(ing) the temperature of multi-functional epoxy compound (D) more than the fusing point of polyamide resin (C) under, preferably under the existence of linking agent, carry out melting mixing, thereby carry out.The amount of halogenation isomeric olefine-to alkylstyrene copolymers rubber (B), take polyamide resin (C) and halogenation isomeric olefine-to the total amount of alkylstyrene copolymers rubber (B), be benchmark, preferably 40 ~ 70 quality %, 45 ~ 65 quality % more preferably.If halogenation isomeric olefine-very few to the ratio of alkylstyrene copolymers rubber (B), tired old weather resistance reduces, otherwise if too much, mobility during melting reduces, and processibility is reduced.
The kind of linking agent and use level, those skilled in the art can carry out suitable selection according to dynamic crosslinking condition.As the example of linking agent, can list zinc oxide, stearic acid, Zinic stearas, magnesium oxide, a phenylenedimaleimide, alkyl phenolic resin and its halogenide, secondary amine, for example N-(1,3-dimethylbutyl)-N '-phenyl-Ursol D etc.Wherein preferably use zinc oxide, stearic acid, Zinic stearas, N-(1,3-dimethylbutyl)-N '-phenyl-Ursol D as the linking agent for dynamic crosslinking.More preferably linking agent contains zinc oxide.The amount of linking agent is typically, with respect to halogenation isomeric olefine-alkylstyrene copolymers rubber (B) 100 mass parts are preferably to 0.1 ~ 12 mass parts, and 3 ~ 9 mass parts more preferably.If the amount of linking agent is very few, dynamic crosslinking is insufficient, can not keep halogenation isomeric olefine-loose to the differential of alkylstyrene copolymers rubber (B), and tired old weather resistance reduces.Otherwise, if the amount of linking agent is too much, can causes occurring incipient scorch in mixing or processing or after masking, produce the bad order of flake (fish eye) etc.
Every 1 molecule of multi-functional epoxy compound (D) has 2 above epoxy group(ing), is preferably that every 1 molecule has 2 ~ 3, more preferably every 1 molecule has two epoxy group(ing).As multi-functional epoxy compound's example, can list 2 functionality epoxy compoundss, such as bisphenol f type epoxy resin, bisphenol A type epoxy resin, ethylene glycol bisthioglycolate glycidyl ether, glycol ether diglycidyl ether, polyoxyethylene glycol diglycidyl ether etc.; 3 functionality epoxy compoundss such as, many glycidyl ethers of glycerol etc.; The more epoxy compounds of polyfunctionality, such as epoxidised soybean oil, epoxidation linseed oil, epoxidized polybutadiene, Sorbitol Powder poly epihydric alcohol base ether etc.Both can use a kind in these multi-functional epoxy compounds, also can be by two or more and use.
Multi-functional epoxy compound's (D) amount is that 0.05 mass parts is above and be less than 3 mass parts, be preferably below above 2 mass parts of 0.05 mass parts with respect to polyamide resin (C) 100 mass parts.When multi-functional epoxy compound's (D) amount is less than 0.05 mass parts with respect to polyamide resin (C) 100 mass parts, a large amount of while filling halogenation isomeric olefines-to alkylstyrene copolymers rubber (B) processibility (mobility) to improve effect little, so not preferred.In multi-functional epoxy compound's (D) amount, with respect to polyamide resin (C) 100 mass parts, be 3 mass parts when above, tired old weather resistance reduces, so not preferred.
In order to improve the consistency of halogenation isomeric olefine with respect to epoxide-modifying polyamide resin (A)-to alkylstyrene copolymers rubber (B), can be before polyamide resin (C) and halogenation isomeric olefine-to alkylstyrene copolymers rubber (B) and multi-functional epoxy compound's (D) melting mixing in advance using as expanding material such as, by anhydride modified olefin copolymer (such as the maleic anhydride modified ethene-copolymers of unsaturated carboxylic acids of maleic anhydride modified ethylene-ethyl acrylate copolymer etc., maleic anhydride modified ethylene-propylene copolymer for example, maleic anhydride modified ethene-butene-1 copolymer, maleic anhydride modified ethene-1-hexene copolymer, the maleic anhydride modified ethene-alpha-olefin copolymer of maleic anhydride modified ethene-1-octene copolymer etc. etc.) with for example, by anhydride modified vinylbenzene-olefin copolymer (maleic anhydride modified styrene-ethylene-butylene-styrene multipolymer, maleic anhydride modified styrene-ethylene-propylene-styrene multipolymer etc.) with polyamide resin and/or halogenation isomeric olefine-alkylstyrene copolymers rubber (B) is mixed or mixing, or expanding material is added in the melting mixing of these compositions (B) ~ (D).Use level to this expanding material, is not particularly limited, and the halogenation isomeric olefine of take is benchmark to the total mass of alkylstyrene copolymers rubber (B), is typically 5 ~ 50 quality %.
In composition for thermoplastic elastomer of the present invention, except mentioned component, can also coordinate carbon black, silicon-dioxide etc. other the resin such as strengthening agent (filler), sulfuration or linking agent, sulfuration or crosslinking accelerator, softening agent, various oil, antiaging agent and the various additives of the common cooperation used of rubber combination.These additives, as long as without prejudice to object of the present invention, just can be with common use level use in the past.
Composition for thermoplastic elastomer of the present invention can by use such as normally used mixing roll in the thermoplastic resin composition's of kneader, Banbury mixer, single-screw intermixing extruder, twin-screw mixer forcing machine etc. preparation by above-mentioned essential component and arbitrarily additive carry out melting mixing and prepare.Melting mixing, is preferably used twin-screw mixer forcing machine to carry out because its productivity is high.Mixing condition will meet used essential component and the arbitrarily type of additive and use level etc., but the lower limit of melting mixing temperature is so long as at least the melt temperature of polyamide resin (C) is above, preferably, higher than 20 ℃ of above high temperature of fusing point, be typically approximately 180 ℃ ~ approximately 300 ℃.The melting mixing time is typically 30 seconds ~ and 10 minutes, be preferably 1 ~ 5 minute.
The melting mixing thing that melting mixing is obtained then becomes the shapes such as membranaceous, sheet or tubulose from the mouth mould extrusion such as being arranged on the relief outlet of twin-screw mixer forcing machine by usual method; or; be extruded into strip; by the first granulating of tablets press for resin; then by the particle obtaining by common resin forming methods such as blow molding, roll-forming, extrusion mouldings, according to purposes, carry out the desirable shapes such as moulding is membranaceous, sheet, tubulose.
Pneumatic tyre of the present invention is to use the composition for thermoplastic elastomer obtained by above-mentioned manufacture method as the pneumatic tyre of air retaining wall.More specifically say and use the film of above-mentioned composition for thermoplastic elastomer or above-mentioned multilayer body as the pneumatic tyre of air retaining wall.As the method for manufacturing tire, can use customary way.For example, composition for thermoplastic elastomer of the present invention is extruded with width and the membranaceous of thickness of regulation, usingd that it is attached to tire building with becoming cylinder on rotary drum as air retaining wall.The parts that the common tire such as the body piles made by unvulcanized rubber, belt, tread ply of fitting successively thereon is again used in manufacturing, take off from rotary drum, obtain green tire.Next this green tire is carried out to baking according to well-established law, produce thus desirable pneumatic tyre.
Composition for thermoplastic elastomer of the present invention can be for the manufacture of flexible pipe.As using composition for thermoplastic elastomer of the present invention to manufacture the method for flexible pipe, can use customary way.For example can manufacture in the following manner flexible pipe.First, use the particle of composition for thermoplastic elastomer of the present invention, by resin extruded machine with pinblock extrusion way extruded thermoplastic elastic composition to push rod, form inner tube.And then extrude on inner pipe other composition for thermoplastic elastomer of the present invention or common thermoplastic rubber composition, outer tube layer in forming.Next, by coating, spraying etc., give caking agent as required on inner pipe.And then, use on inner pipe braiding machine that reinforcement silk or reinforcement steel wire are woven.The caking agent of coating for engaging with outer tube on strengthening course, then extrudes by the resin of pinblock composition for thermoplastic elastomer of the present invention or other common thermoplastic rubber composition equally with forcing machine as required, forms outer tube.Finally extract push rod out, obtain flexible pipe.Caking agent as coating on inner pipe or on strengthening course, can list isocyanate-based, carbamate system, resol system, Resorcinol system, chlorinated rubber system, HRH system etc., particularly preferably isocyanate-based, carbamate system.
Embodiment
With reference to embodiment and comparative example shown below, the present invention is more specifically described, but scope of the present invention is not limited by these embodiment, this is needless to say more.
In the manufacture of the composition for thermoplastic elastomer of embodiment 1 ~-3 and comparative example 1 ~ 3, use following material.
material
Halogenation isomeric olefine-to alkylstyrene copolymers rubber (bromination iso-butylene-p-methylstyrene copolymer rubber): Exxpro (registered trademark) the MD X89-4 (hereafter is " Br-IPMS ") of エ Network ソ Application モ mono-ビル ケミカル society (ExxonMobil Chemical Company) system
Polyamide resin: the nylon 6/66 (UBE nylon 5013B) of space Bu Xing Chan Zhushihui company system
Multi-functional epoxy compound 1: bisphenol f type epoxy resin (YDF-170,2 functionalities of Nippon Steel's chemistry (strain) system)
Multi-functional epoxy compound 2: epoxidised soybean oil (エ Port サ イ ザ mono-W100-EL of DIC (strain) system)
Zinc oxide: 3 kinds, the zinc oxide of just same chemical industry (strain) system
Stearic acid: the stearic acid pearl of day oil (strain) system
Zinic stearas: Sakai chemical industry (strain) system
Expanding material: maleic anhydride modified ethylene-ethyl acrylate copolymer (the HPR AR201 of Mitsui デ ユ Port Application Port リ ケ ミ カ Le (strain) system)
the manufacture of the composition for thermoplastic elastomer of comparative example 1
Use hermetic type Banbury mixer ((strain) Kobe Steel is made) with the cooperation shown in following table 1, rubber and linking agent (zinc oxide, stearic acid and Zinic stearas) to be mixed 2 minutes at 100 ℃; make rubber composite, by rubber comminutor ((strain) gloomy mountain makes made), be processed into particulate state.By the particle of the rubber composite obtaining and polyamide resin and expanding material by twin-screw mixer machine ((strain) JSW system) at 250 ℃ mixing 3 minutes.Melting mixing thing is extruded into strip continuously from forcing machine, with water cooling, cuts machine and be cut into particulate state, obtain thus granular composition for thermoplastic elastomer.Comparative example 1 is not contain the example of the thermoplastic elastomer of epoxy compounds.
the manufacture of the composition for thermoplastic elastomer of embodiment 1 ~ 3 and comparative example 2 ~ 3
Use hermetic type Banbury mixer ((strain) Kobe Steel is made) with the cooperation shown in table 1, rubber and linking agent (zinc oxide, stearic acid and Zinic stearas) to be mixed 2 minutes at 100 ℃; make rubber composite, by rubber comminutor (gloomy mountain makes made), be processed into particulate state.Use twin-screw mixer machine ((strain) JSW system) by the particle of the rubber composite obtaining and polyamide resin and expanding material at 250 ℃ mixing 3 minutes.Now use and add the long containing of liquid pump (Sickle (strain) system) epoxy compounds is added in melting mixing thing.Melting mixing thing is extruded into strip continuously from forcing machine, with water cooling, cuts machine and be cut into particulate state, obtain thus granular composition for thermoplastic elastomer.
test method
(1) mixing property
When manufacturing the composition for thermoplastic elastomer of embodiment and comparative example, observe composition for thermoplastic elastomer and its outward appearance of from twin-screw mixer forcing machine, with strip, extruding, according to the mixing property of following benchmark evaluation respectively.
Good: the smooth surface of bar.
Can: observe the slightly granular flaw in the surface of bar or coarse, or slightly the pulsation of bar is discharged.
Bad: the surface irregularity of bar, the remarkable discharge of observing bar is bad.
(2) thermostability
Thermostability is each composition for thermoplastic elastomer for embodiment 1 ~ 3 and comparative example 1 and 2, obtains in the following manner respectively velocity of variation and (ii) extrusion moulding that (i) kapillary is sheared viscosity, thereby evaluate.The composition for thermoplastic elastomer of comparative example 3, the discharge of bar is significantly bad, so do not have assess thermal stability and tired old weather resistance.
(i) kapillary is sheared the velocity of variation of viscosity
In the mensuration of kapillary shearing viscosity, use Japan's essence machine (strain) capillary rheometer キ processed ヤ ピ ロ グ ラ Off 1C, at velocity of shear 243sec
-1, 250 ℃ of temperature, under 5 minutes and 10 minutes hold-time, use the orifice of diameter 1mm * length 10mm to measure the melt viscosity (unit: Pas) of composition for thermoplastic elastomer.The viscosity obtaining while usining 5 minutes hold-times is as benchmark, and the difference of the viscosity that the viscosity obtaining when the hold-time is 10 minutes and hold-time obtain while being 5 minutes is expressed as percentage, as velocity of variation.When velocity of variation is less than 20%, for good, velocity of variation is more than 20% to be bad.
(ii) extrusion moulding
Use T-shaped mould extrusion molding apparatus (Mould Breadth: 200mm) composition for thermoplastic elastomer is extruded at 220 ℃ of temperature to the sheet of thickness 1mm.At shaped device, turn round afterwards, shut down 3 minutes temporarily, and then start the running of shaped device.The outward appearance of the extrudate piece obtaining after the outward appearance of the extrudate piece obtaining before the running of observation shaped device stops and running start again, the thermostability during with following benchmark evaluation moulding.
Good: the extrudate piece obtaining before stopping with running is compared, the outward appearance of the extrudate piece obtaining after running starts again does not change.
Can: observe the slightly granular flaw of extrudate piece that obtains after running starts again or surface irregularity slightly.
Bad: observing the extrudate piece obtaining after running starts again has a large amount of granular flaw or surperficial waste rough.
(3) tired old weather resistance
Composition for thermoplastic elastomer is shaped to the sheet of thickness 1mm, by the sheet stamping-out obtaining, becomes JIS#3 dumbbell shaped sample.Use the old trier that surely should weaken (upper island makes made) to the sample obtaining in temperature-25 ℃ and strain rate repeatedly apply fatigue 40% time until 1,000,000 times.For the composition for thermoplastic elastomer of embodiment and comparative example, measure respectively 12 samples, the number of times when disrumpent feelings is carried out to Wei Boer distribution, the point that is 63% using disrumpent feelings probability is as tired old weather resistance.Number of times before disrumpent feelings is more, represents that tired old weather resistance is more excellent.
Above-mentioned test-results is shown in to following table 1.
According to above-mentioned test-results, can judge, although the composition for thermoplastic elastomer of embodiment 2 is observed slightly granular flaw in the evaluation of mixing property, embodiment 2 and 3 tired old weather resistance reduce, but be all in the scope that can allow, the mixing property of composition for thermoplastic elastomer of the present invention (embodiment 1 ~ 3), thermostability, tired old excellent in te pins of durability.On the other hand,, containing multi-functional epoxy compound's comparative example 1 and multi-functional epoxy compound's the use level comparative example 2 fewer than scope of the present invention, thermostability is all not bad.Multi-functional epoxy compound's use level is more than the comparative example 3 of scope of the present invention, and the discharge of bar is significantly bad.
Industry utilizability
Composition for thermoplastic elastomer of the present invention is suitable for airtyred air retaining wall.In addition, composition for thermoplastic elastomer of the present invention, except for pneumatic tyre, can also be used as the barrier material that flexible pipe, wharf fender, rubber bag, tanks etc. need the rubber laminate of barrier properties for gases.
Claims (8)
1. a composition for thermoplastic elastomer, it has external phase and disperse phase, and external phase contains (A) epoxide-modifying polyamide resin, and disperse phase contains (B) halogenation isomeric olefine-to alkylstyrene copolymers rubber, this composition for thermoplastic elastomer is characterised in that, is by inciting somebody to action
(B) halogenation isomeric olefine-to alkylstyrene copolymers rubber,
(C) polyamide resin and
(D) with respect to 100 mass parts polyamide resins (C) be 0.05 mass parts above and be less than 3 mass parts, every 1 molecule has the multi-functional epoxy compounds of 2 above epoxy group(ing)
Melting mixing at temperature more than the fusing point of polyamide resin (C), thereby obtain,
Epoxide-modifying polyamide resin (A) is by the reaction between polyamide resin (C) and multi-functional epoxy compound (D), to generate in described melting mixing.
2. composition for thermoplastic elastomer as claimed in claim 1, polyamide resin (C) is selected from nylon 11, nylon 12, nylon 6, nylon 66, nylon 6/66, nylon 6/12, nylon 6/10, nylon 4/6, nylon 6/66/12, aromatic nylon and two or more combination in them.
3. composition for thermoplastic elastomer as claimed in claim 1 or 2, halogenation isomeric olefine-to alkylstyrene copolymers rubber (B), be bromination iso-butylene-p-methylstyrene copolymer rubber.
4. composition for thermoplastic elastomer as claimed in claim 1 or 2, halogenation isomeric olefine-to alkylstyrene copolymers rubber (B), be that dynamic crosslinking forms.
5. composition for thermoplastic elastomer as claimed in claim 1 or 2, halogenation isomeric olefine-to alkylstyrene copolymers rubber (B), be that dynamic crosslinking forms under the existence of the linking agent that contains zinc oxide.
6. composition for thermoplastic elastomer as claimed in claim 1 or 2, take polyamide resin (C) and halogenation isomeric olefine-to the total amount of alkylstyrene copolymers rubber (B), be benchmark, halogenation isomeric olefine-to the amount of alkylstyrene copolymers rubber (B), be 40～70 quality %.
7. the manufacture method of the composition for thermoplastic elastomer described in any one of claim 1～6, described composition for thermoplastic elastomer has external phase and disperse phase, external phase contains (A) epoxide-modifying polyamide resin, disperse phase contains (B) halogenation isomeric olefine-to alkylstyrene copolymers rubber, described manufacture method is characterised in that, comprises following operation: will
(B) halogenation isomeric olefine-to alkylstyrene copolymers rubber,
(C) polyamide resin and
(D) with respect to 100 mass parts polyamide resins (C) be 0.05 mass parts above and be less than 3 mass parts, every 1 molecule has the multi-functional epoxy compounds of 2 above epoxy group(ing)
Melting mixing at temperature more than the fusing point of polyamide resin (C).
8. a pneumatic tyre, in air retaining wall, right to use requires the composition for thermoplastic elastomer described in 1～6 any one.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010144833A JP5736677B2 (en) | 2010-06-25 | 2010-06-25 | Thermoplastic elastomer composition and method for producing the same |
| JP144833/2010 | 2010-06-25 | ||
| PCT/JP2011/053430 WO2011161981A1 (en) | 2010-06-25 | 2011-02-10 | Thermoplastic elastomer composition and manufacturing method therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102725353A CN102725353A (en) | 2012-10-10 |
| CN102725353B true CN102725353B (en) | 2014-08-27 |
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| CN201180007088.4A Expired - Fee Related CN102725353B (en) | 2010-06-25 | 2011-02-10 | Thermoplastic elastomer composition and manufacturing method therefor |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US8933172B2 (en) |
| EP (1) | EP2586829A4 (en) |
| JP (1) | JP5736677B2 (en) |
| CN (1) | CN102725353B (en) |
| WO (1) | WO2011161981A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9334984B2 (en) * | 2012-06-06 | 2016-05-10 | Saint-Gobain Performance Plastics Corporation | Thermoplastic elastomer tubing and method to make and use same |
| JP6044245B2 (en) * | 2012-10-03 | 2016-12-14 | 横浜ゴム株式会社 | Method for producing film-like member for pneumatic tire |
| US20180179372A1 (en) * | 2015-07-28 | 2018-06-28 | Exxonmobil Chemical Patents Inc. | Elastomeric Compositions and Their Use in Articles |
| US11833750B2 (en) | 2018-09-22 | 2023-12-05 | Hewlett-Packard Development Company, L.P. | Three-dimensional printing |
| WO2020197261A1 (en) * | 2019-03-28 | 2020-10-01 | 롯데케미칼 주식회사 | Polyamide resin composition and molded product comprising same |
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- 2011-02-10 US US13/639,445 patent/US8933172B2/en not_active Expired - Fee Related
- 2011-02-10 EP EP11797869.2A patent/EP2586829A4/en not_active Withdrawn
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2586829A1 (en) | 2013-05-01 |
| US20130030124A1 (en) | 2013-01-31 |
| CN102725353A (en) | 2012-10-10 |
| WO2011161981A1 (en) | 2011-12-29 |
| US8933172B2 (en) | 2015-01-13 |
| EP2586829A4 (en) | 2015-08-12 |
| JP2012007092A (en) | 2012-01-12 |
| JP5736677B2 (en) | 2015-06-17 |
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